Copolymers of alpha, beta-ethylenically unsaturated phosphonic acid derivatives



Patented 'Apnifi, 1948 I d COPOLYMERS F ALPHA,BETA-ETHYLENI- CALLY UNSATURATED PHOSPHONIC ACID DERIVATIVES Richard Vernon Lindsey, Jr., Wilmington, DeL,

assignor to E. I. du Pont de Nemours 8: Company, Wilmington, Del., a corporation oi Delaware No Drawing. Application May 11, 1944, Serial No. 535,197

8 Claims. 1

This invention relates to new compositions of matter and more particularly to new plastic compostions. More specifically, this invention relates to polymers of alpha,beta-ethylenically un- 2 parent, plastic sheet. Complete polymerization may also be effected on heating the same reaction charge for 24 hours at 65 C.

saturated phosphonic acid derivatives. h Example H Alpha,beta-ethylenical1y unsaturated p osphonic acid compounds including the acids, their 2 352ffi gg gg ggs gfiga gg 23: 25 esters.and t amldes have been found to be tive ingredient) and 111 cc. of water was charged essentially unpolymerizable by themselves in i t a t1 1 m with m l t spite of numerous attempts, Attempts to poly- ,2 3* f z g fg g PM add c if; meflzethese compounds ii-methyl l-pm' :5 111311571 n ethazrylate $2122 of d nethg? 1 pene'z'phosphonateand 'dlmethyl'bpm' propene-Z-phosphonate, and 0.6 part of ammonipene-2-phosphonam1cle with chloroprene have um r ulf t t 1 t Th f i the been completel unsuccessful. Polymerizations v z 5 s ca 23 h g 1;; sli ice n th of such compounds with butadiene have met with es 1 d gi 8 5? 9 but little success. .It was therefore surprising to "5 g 28: 3 ed Y 2gdiscover that these compounds interpolymerize 212 a d t e 1 8 satisfactorily with polymerizable compounds r zzgf g ggi r g ga g"; g gg containing one, but only one CH2= group, i, e. parts of 107 M f i g 3; E with polymerizable vinyl and vinyllden comfine owde 1 er wa 'g pounds containing but one ethylenic double bond. t t 5 ym 5 g 3 It is an object of this invention to provide a 2 5 1 3 2 .difipers ng g ts valuable new class of interpolymers of alpha, 2 was a y $2 r q, 8 en beta-ethylenically unsaturated phosphonic acid n a g a g Pours t are derivatives with polymerizable mono-ethylenic m g z s ft iil 1 2 231303 ain compounds. Further objects will appear hereini q i 'gg' fig gg g after.

These objects are accomplished by the followproperties Moldmgs of this polymer were very ing invention which comprises heating an alpha, 0 clear with only faint yelmwish tint' beta-ethylenically unsaturated phosphonic acid, 3 ester, or amide, with one or more polymerizable Example monovinyl or monovinylidene compounds in the A Solution of 7.8 parts of commercial sodium Presence of an Oxygen-liberating catalyst a cetylsulfate paste (23% active ingredient) and temperature and for a time suflicient to bring 05 part of ammonium persulfate m 111 parts of about polymerization and isloating the resultant water was charged into a reaction vessel equipped polymer The polymerization may be conducted with a mechanical agitator. The free space in in 19 9 emulsion, in bulk or in granular poly the vessel was flushed with nitrogen and a monomerlzatlon m mer mixture comprising 51 parts of methyl meth- The more detailed practice of the invention i acrylate and nine parts f NN,N'N' tetramethy1 illustrated by the following examples, wherein 40 1 pr0pene 2 ph0sphondiam1de was added- The parts are by Weight There of course many vessel was sealed,'heated to C and mainforms of the invention other than these specific tamed at this temperature for a berlodof 47 m n hours. At the end 01' this time, the resulting Example I 45 polymer dispersion was removed from the reaction vessel, steamed to remove unreacted mono- Nine (9) parts of dimethyl 1-propene-2-phosmers and treated with 20 parts of 10% aluminum phonate, 51 parts of methyl methacrylate and sulfate solution. The resulting coagulated poly- 0.6 part of benzoyl peroxide were charged into mer was filtered and washed by conventional a glass-lined reaction vessel. The vessel was then procedures and dried in vacuoat C. There flushed with nitrogen and the contents heated was obtained 53 parts of a polymer softening at to 45 C. for a period of 48 hours. A clear solid 111 C. and containing 0.57% phosphorus. Atcake of interpolymer containing 3.00% phostractive moldings were prepared by subjecting phorus was obtained in quantitative yield. The the polymer to 1,000 pounds pressure at 160 C. polymer was converted by molding at elevated for one minute in asuitable die. Attractive, clear temperatures and pressure to a tough, transmolded articles were obtained.

Example IV Example V A stainless-steel-lined, pressure-resistant vessel was charged with 100 parts of water, ten parts of dimethyl l-propene-2-phosphonate and 02 part of benzoyl peroxide. The vessel was closed, evacuated to remove residual air, placed in a shaker machine provided with a heater, pressured with ethylene, and heating and agitation were started. During a reaction time of 9.25 hours, throughout which the temperature was maintained at 74 to 76 C. and the pressure at 860 to 940 atmospheres, there was a tot-a1 observed pressure drop of 145 atmospheres. The vessel was then cooled, bled of excess ethylene, opened and the contents discharged. The reaction mixture was filtered and the precipitate was washed continuously with water for one hour in a basket centrifuge. The polymer was then dried and there was thus obtained 13 parts of an ethylene/dimethyl l-propene-2-phosphonate copoly mer which contained 7.11% phosphorus from which it is calculated that the ethylene/ ester mole ratio was 10.2/ 1. The relative viscosity as determined on a 0.125% solution in xylene at 85% C. was 1.04 which corresponds to an intrinsic viscosity of 0.31 and to a molecular Weight (using Staudingers hydrocarbon constant) of approximately 2.640.

- Tests of this material as an oil adjuvant showed methyl 1-propene-2-phosphonate and 0.3 part of benzoyl peroxide. The pH of this mixture was adjusted from6.1 to 8.4 by the addition of a few drops of dilute formic acid. The reaction was carried out substantially as in Example V. In a reaction time of 9.5 hours, throughout which the temperature was maintained at 73 to 78 (Land the pressure at 760 to 950 atmospheres, there was a total observed pressure dropof 425 atmospheres. The polymer was isolated as in Example V. There was thus obtained 28 parts of an ethylene/di- -methyl 1 propene 2 phosphonate copolymer which contained 2.3% phosphorus, corresponding to an ethylene/ ester mole ratio of 42/1 and which had an intrinsic viscosity of 0.79 and a tensile strength at break of 1,290 lbsJsq. in. (original dimensions) at 215% elongation. Films of this copolymer could be readily cold drawn to 575% of their original length. They showed excellent tear resistance.

By substituting diphenyl 1-propene-2-phosphonate and 1-phenylethylene-l-phosphonic acid respectively, for dimethyl 1-propene-2-phosphonate in Example VIII, the corresponding copolymers of these compounds with ethylene were prepared.

Although in the foregoing examples certain definite interpolymer combinations, conditions of polymerization and reaction temperatures have been described, it is to be understood that these in no way limit the invention within the spirit and scope thereof. Broadly speaking, this invention contemplates the preparation of interpolymers of -alpha,beta-ethylenically unsaturated phosphonic acids and derivatives by the interpolymerization of alpha,beta-ethylenically unsaturated phosphonic acids and derivatives with polymerizable compounds having but one CH2=C group, i. e. monovinyl and monovinylidene compounds, according to the bulk, granulathat 0.5% of the polymer in lubricating oil approximately halved the oxygen absorption rate and lowered the pour pointfrom 30 to 0 F., while a 1% concentration of polymer in lubricating oil raised the film strength (Cornell test) from 900 lbs./ sq. in. to 1,750 lbs/sq. in.

Example VI Example VII A stainless-steel-lined, pressure-resistant vessel was charged with 100 parts of water, 20 parts of dibutyl 1-propene-2-phosphonate and 0.2 part of benzoyl peroxide. Reaction was carried out under substantially the conditions of Example V and the reaction mixture yielded 21 parts of an ethylene/dibutyl l-propene-Z-phosphonate copolymer which contained 5.6% phosphorus and had an intrinsic viscosity of 0.24. From this analysis, it is calculated that the copolymer had, an ethylene/ester mole ratio of 11.2/1.

Example VIII A silver-lined, pressure-resistant vessel was charged with 100 parts of water, 4 parts of dition or emulsion polymerization techniques known to the art. Depending on the conditions of polymerization selected, the formation of polymer may occur at temperatures between about 20 C. and 120 (2., preferably in the presence of an oxygen-liberating catalyst, such as benzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium 'perborate, peroxydisuccinic acid, diethyl peroxide and the like. If the bulk polymerization technique is employed, it is preferred to use a soluble peroxide catalyst of the v type represented by benzoyl peroxide. Aqueous emulsion polymerizations are best carried out in the presence of soluble persulfate salts. The choice of specific conditions of polymerization will of course be governed by the type and kind of product desired and the uses to which it is to be put. In general, bulk polymerized products are clear, tough plastics whereas those produced in emulsion may contain impurities introduced from the dispersing agent or'catalyst which are difficult to remove. For many uses, however, these impurities present no disadvantage.

Depending on the type of monomer selected for the polymerization, the process may be carried out under atmospheric pressure or under superatmospheric pressures in closed equipment. It is desirable to flush the polymerization vessel with an inert gas, such asnitrogen, in order to exclude air from the polymerization system. J

In emulsion polymerizations, it is preferred to use synthetic dispersing agents, such as long chain alkyl sulfuric ester salts, soluble salts of sulfonated long chain hydrocarbons, salts of alkylated naphthalenesulfonic acids, soaps of saturated or unsaturated fatty acids, and soluble salts oi sulfonated oleic esters; Other types of dispersing agents may also be used, depending on the nature of the vinyl or vinylidene monomers chosen for copolymerization with the unsaturated phosphonic acid derivatives.

The alpha,beta-ethylenically unsaturated phosphonic acid derivatives coming within the scope of this invention are exemplified by 1-propene-2- phosphonic acid, the dialkyl esters of l-propene- 2-phosphonic acid, e. g. dimethyl and dibutyl 1- propene-2-phosphonates, and the N,N,N',N'- tetraalkyl-1-propene-2-phosphondiamides, e. g. N,N,N',N' tetramethyl 1 propene 2 phosphondiamide. Other alpha,beta-ethylenically unsaturated phosphonic acids, esters and amides may be employed. A preferred group are the.

alkene phosponic acids and derivatives in which the phosphono roup is attached to one of the double bonded carbons and which have the following general formula:

wherein X equals OH, OH.

and R. R R and R are hydrogen or alkyl radicals, R is an alkyl radical and R is an alkyl or aryl radical. These alpha,beta-ethylenically unsaturated phosphonic acid derivatives can be prepared according to the processes described in Hamilton U. S. Patent 2,365,466 which issued on application Serial No. 463,079, filed October 23, 1942; the disclosure of which is hereby incorporated. Other acids, esters and amides of these l-alkene-Z-phosphonic acids are the diethyl, diamyl, dibenzyl, and diphenyl esters and the N,N,N',N'-tetraethyl-, N,N,N'N'-tetrabutyl-, N,N,N,N' tetraamyl-, N,N,N'.N' tetrabenzyl-, and the N,N,N,N' tetraphenyl 1 propene-Z phosphondiamides.

The invention is generic to interpolymers and interpolymerization of the phosphonic acid derivatives as above set forth, with polymerizable organic compounds having one, and only one CH2=C group, i. e. with monovinyl and monovinylidene compounds exemplified by methyl acrylate, methyl methacrylate, higher alkyl methacrylates, styrene, ethylene, acrylonitrile, vinyl chloride, vinyl acetate, vinylidene chloride and N-vinyl compounds, such as N-vinyl imides and N-vinyl amides. The proportion of the phosphonic acid and derivatives can be varied between 95% and 5% of the total polymerization mixture with corresponding amounts of the appropriate vinyl or vinylidene monomers. In addition, interpolymer systems involving two or more monovinyl and monovinylidene compounds in combination with the unsaturated phosphonic acid derivatives may be used to give valuable products.

The polymers of this invention are useful as molding plastics, for films, fibers and coating compositions for metals, fabrics and leather. Products containing the phosphonic acid derivatives are characterized by excellent clarity and by good stability on exposure to heat and light.

I The above'description and examples are inincluded within the scope of the claims.

What is claimed is:

1. An interpolymer of dimethyl 1-propene-2- phosphonate with methyl methacrylate containirig 5-95% dimethyl 1-propene-2-phosphonate and 95-5% methyl methacrylate.

2. An interpolymer of 5 to 95% methyl methacrylate with 95-5% or a dialkyl 1-propene-2- phosphonate.

3. An interpolymer oi 5-95% of a phosphonic compound of the class consisting of dialkyl esters, diaryl esters and tetraalkyldiamides or alkene phophonic acids in which acids the phosphorus is bonded to carbon or an alkenyl radical, said carbon being ethylenically doubly bonded to a second carbon of said radical, and 95-5% of a comonomer of the class consisting of alkyl methacrylates, methyl acrylate, styrene, ethylene, acrylonitrile; vinyl chloride, vinyl acetate, and vinylidene chloride.

4. An interpolymer according to claim 3 wherein the comonomer is an alkyl methacrylate.

5. An interpolymer according to claim 3 wherein the comonomer is methyl methacrylate. 6. An interpolymer of an alkyl ester of an alkene-phosphonic acid in which the phosphorus is bonded to carbon of an alkenyl radical, said carbon being ethylenically doubly bonded to a second carbon of said radical, said interpolymer containing 5-95% of said ester, the remainder of said interpolymer consisting of a comonomer of th class consisting of alkyl methacrylates, methyl acrylate, styrene, ethylene, acrylonitrile, vinyl chloride, vinyl acetate, and vinylidene chlo-,

' ride.

in the alkyl ester is dimethyl l-propene-Z-phosphonate.

RICHARD VERNON LINDSEY, JR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date OTHER REFERENCES Chem. Abst, vol. 35, page 3963 (1941).

Kosolapoif Nov. 20, 1945 Certificate of Correction I Patent N 0. 2,439,214} 3 I April 6, 1948. RICHARD VERNON LINDSEY, JR. It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Column 1, line 19,-for CH oup reed 0H =U gr0up; column 3, line 34, for 85%' C. read 85 0.; line 38, or the number 2.640 read 2,640; column 6, line 23, claim 3, for phophonic read phosphom'c; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 1st day of June, A. D. 1948.

' THOMAS F. MURPHY,

Assistant Gem/mission of Patents. 

